臺灣博碩士論文加值系統

本實驗室近期利用異香草醛 1a 和 3-羥基苯甲醛 1b 進行了許多合成上的應用1。本篇則闡述利用簡單的合成路線多元化地建構苯駢屈之骨架。其中以異香草醛 1a 和 3-羥基苯甲醛 1b 當作苯駢屈之 A 環，首先進行丙烯基化反應，然後通過克萊森重排來建構 D 環；格裡納加成反應來建構 E 環；鹼性催化下進行環化脫水來建構 B 環；最後利用照光環化反應來建構 C 環；經由 A→D→E→B→C 之順序來完成苯駢屈之骨架，且得到不錯的總產率。(圖一)

Recently, we used isovanillin (1a) and 3-hydroxybenzaldehyde (1b) to complete the numerous synthetic strategies.1 A facile synthetic route toward diversified benzo[g]chrysenes (2) is described in this paper. The isovanillin (1a) and 3-hydroxybenzaldehyde (1b) are the A-ring motif of benzo[g]chrysenes, followed by O-allylation, Claisen rearrangement to construct the D-ring, Grignard addition to construct the E-ring, DBU-promoted cyclodehydration to construct the B-ring, and photolytic Scholl oxidative annulation to construct the C-ring. The benzo[g]chrysenes skeleton is successfully constructed through a novel synthetic sequence of A?蛇?蛀?處?彪 approach and acquire a modest total yields. (fig 1)

中文摘要………………………………………………………………1

英文摘要………………………………………………………………2

研究動機簡介…………………………………………………………3

結果與討論……………………………………………………………11

結論……………………………………………………………………27

實驗部分………………………………………………………………29

實驗步驟和數據………………………………………………………32

參考文獻………………………………………………………………85

附錄…………………………………………………………………….88

1. (a) Chang, M.-Y.; Lee, N.-C. Synlett 2012, 867; (b) Chang, M.-Y.; Wu, M.-H.; Lee, N.-C.; Lee, M.-F. Tetrahedron Lett. 2012, 53, 2125; (c) Chang, M.-Y.; Wu, M.-H. Tetrahedron Lett. 2012, 53, 3173; (d) Chang, M.-Y.; Wu, M.-H.; Lee, T.-W. Tetrahedron 2012, 68, 6224; (e) Chang, M.-Y.; Wu, M.-H.; Chen, Y.-L. Tetrahedron Lett. 2012, 53, 4156; (f) Chang, M.-Y.; Tai, H.-Y.; Chen, Y.-L.; Hsu, R.-T. Tetrahedron 2012, 68, 7941; (g) Chang, M.-Y.; Wu, M.-H.; Tai, H.-Y. Org. Lett. 2012, 14, 3936; (h) Chang, M.-Y.; Wu, M.-H. Tetrahedron 2012, 68, 9616; (i) Chang, M.-Y.; Chan, C.-K.; Lin, S.-Y.; Hsu, R.-T. Tetrahedron 2012, 68, 10272.
2. (a)Wu, J.; Pisula,W.; Mullen, K. Chem. Rev. 2007, 107, 718; (b) Karitzky, A. R.; Li, J.; Xie, L. Tetrahedron 1999, 55, 8263.
3. (a)Ronald G. Harvey. Tetrahedron 2012, 68, 7217; (b) Science 1976, 193, 592 .
4. (a) Sukumaran, K. B.; Harvey, R. G. J. Org. Chem. 1981, 46, 2740; (b) Harvey, R. G. Tetrahedron Lett. 1995, 36, 6037; (c) Wu, A.; Xu, D.; Lu, D.; Penning, T. M.; Blair, I. A.; Harvey, R. G. Tetrahedron 2012, 68, 7217.
5. (a) Krzeminski, J.; Hecht, S. S. Chem. Res. Toxicol. 1994, 7, 125; (b) Sayer, J. M.; Yagi, H.; Croisy-Delcey, M.; Jerina, D. M. J. Am. Chem. Soc. 1981, 103, 4970.
6. Bushman, D. R.; Grossman, S. J.; Jerina, D. M.; Lehr, R. E. J. Org. Chem. 1989, 54, 3533.
7. Kiselyov, A. S.; Lee, H.; Harvey, R. G. J. Org. Chem. 1995, 60, 6123.
8. Kumar, S. J. Org. Chem. 1997, 62, 8535.
9. (a) Shimizu, M.; Hiyama, T. Tetrahedron 2011, 67, 8014; (b) Yamaguchi, S.; Swager, T. M. J. Am. Chem. Soc. 2001, 123, 12087; (c) Sharma, A. K.; Amin, S. J. Org. Chem. 2004, 69, 3979; (d) Chaudhuri, R.; Liu, R.-S. Org. Lett. 2008, 10, 3053;
10. (a) Harvey, R. G. J. Org. Chem. 2004, 69, 1372; (b) Zhang, F.-J.; Harvey, R. G. J. Org. Chem. 2000, 65, 3952.
11. Ana M. Martı ́n Castro. Chem. Rev. 2004, 104, 2939−3002
12. (a) De Koning, C. B.; Rousseau, A. L. Tetrahedron Lett. 1997, 38, 893; (b) De Koning, C. B.; Manzini, S. S.; Michael, J. P.; Mmutlane, E. M.; Tshabidi, T. R.; Van Otterlo, W. A. L. Tetrahedron 2005, 61, 555; (c) Sibi, M. P.; Dankwardt, J. W.; Snieckus, V. J. Org. Chem. 1986, 51, 271; (d) Rao, B. B.; Wei, J.-R.; Lin, C.-H. Org. Lett. 2012, 14, 3640.
13. (a) Boden, N.; Bushby, R. J.; Headdock, G.; Lozman, O. R.; Wood, A. Liq. Cryst. 2001, 28, 139; (b) King, B. T.; Kroulik, J.; Robertson, C. R.; Rempala, P.; Hilton, C. L.; Korinek, J. D.; Gortari, L. M. J. Org. Chem. 2007, 72, 2279; (c) Simpson, C. D.; Mattersteig, G.; Martin, K.; Gherghel, L.; Bauer, R. E.; Rader, H. J.; Mullen, K. J. Am. Chem. Soc. 2004, 126, 3139; (d) Navale, T. S.; Thakur, K.; Rathore, R. Org. Lett. 2011, 13, 1634; (e) Zhang, X.; Jiang, X.; Zhang, K.; Mao, L.; Luo, J.; Chi, C.; Chan, H. S. O.; Wu, J. J. Org. Chem. 2010, 75, 8069.